Polymeric bicyclohexyl - 4,4&#39; - dimethylene-4,4&#39;-bibenzoates and related linear polymers



United States Patent POLYMERIC BICYCLOHEXYL 4,4 DIMETHYL-ENE-4,4'-BIBENZOATES AND RELATED LINEAR POLYMERS Robert G. Thompson,Kinston, N.C., assignor to E. I. du Pont de Nemours and Company,Wilmington, Del., a corporation of Delaware No Drawing. Originalapplication Mar. 13, 1963, Ser. No. 264,783, now Patent No. 3,467,719,dated Sept. 16, 1969. Divided and this application Oct. 18, 1965, Ser.No. 509,245

Int. Cl. C08g 17/08, 20/30 U.S. Cl. 26075 11 Claims ABSTRACT OF THEDISCLOSURE The application discloses a class of glycols containing twohydroxycyclohexyl groups, and linear condensation polymers preparedtherefrom which are characterized by recurring units of the formulawherein m and n are 0 or 1, Q and Q are 1,3- or 1,4- cyclohexylene oralkyl derivatives thereof, R is an alkylene radical, and A is anarylene, aralkylene or cycloalkylene radical preferably containing two6-membered carbocyclic nuclei. Polyesters and polyesteramidesparticularly suitable for textile fibers are illustrated.

This is a division of my application Ser. No. 264,783, filed Mar. 13,1963, which is a continuation-in-part of my application Serial No.187,982 filed Apr. 16, 1962, and now abandoned. The invention relates toa novel class of alicyclic glycols of high molecular weight. Moreparticularly, it relates to glycols containing at least 14 carbon atomsand characterized by the presence of two hydroxymethylcyclohexyl groups.The invention also comprehends novel esters, including polyesters andpolyesteramides, prepared from the glycols, as well as to fibers, films,and other shaped articles produced from the polymers.

In general, the present invention comprehends glycols and esters thereofwherein the glycol contains two hydroxymethylcyclohexyl groups, anyadditional constituents of the glycol being selected from the classconsisting of ether oxygen and saturated hydrocarbon groups having atotal of up to 8 carbon atoms, including the class of'bis(hydroxymethylcyclohexyl)alkanes having up to 22 total carbon atomsand esters thereof.

It has now been found that these glycols can be prepared readily andthat they have excellent utility for reaction with dicarboxylic acids orester-forming derivatives thereof to prepare linear condensationpolyesters or polyesteramides. The noved polyesters are characterized bygenerally high melting points and are particularly adapted for thepreparation of fibers, films, tapes, and the like as well as othershaped articles obtained by using the polyesters as moldingcompositions.

3,492,272 Patented Jan. 27, 1970 One embodiment of the inventioncomprises glycols containing two 2-(hydroxymethyl)cyclohexyl groups, anyadditional constituents of the glycol being selected from the classconsisting of ether oxygen and saturated hydrocarbon groups having atotal of up to 8 carbon atoms. Polyesters and polyesteramides preparedfrom these glycols or their esters are especially useful for formingfilms, molded articles, and the like.

Another embodiment of the invention comprises the class of glycolshaving the general formula:

wherein Q and Q are saturated divalent hydrocarbon radicals of the groupconsisting of 1,3-cyclohexylene, l, 4-cyclohexylene, and lower alkylderivatives thereof; m is 0 or 1; and R is a saturated divalenthydrocarbon radical of 1 to 8 carbon atoms. Preferably a chain of carbonatoms connecting the said Q and Q radicals contains not more than 4carbon atoms. R may therefore represent any alkylene radical of up to 8carbon atoms, either straight chain, branched chain, or cyclic.Polyesters or polyesteramides prepared from these glycols or theiresters are useful not only for films and molded articles but also areespecially useful for forming fibers. A preferred class of glycols,particularly useful as components of such fiber-forming polymers, arethe bis(4-hydroxymethylcyclohexyl)alkanes of up to 22 carbon atomsrepresented by the formula:

wherein m and R are defined as above.

A useful general method for obtaining the novel glycols comprises atwo-stage reduction of the corresponding bibenzoic acids or*bis(carboxyphenyl)alkanes or ethers, involving reduction of thearomatic (benzene) nuclei to alicyclic (cyclohexane) nuclei followed byreduction of the carboxyl groups to hydroxymethyl group's. Reduction ofthe benzene nuclei is conveniently achieved by hydrogenation of an esterof the acid using platinum oxide or ruthenium as a catalyst; whilereduction of the carboxylate groups of the resulting alicyclic ester isreadily obtained by hydrogenation with a catalyst such as copperchromite or by reaction with lithium aluminum hydride. The glycolproducts so obtained consist in each case of a mixture of variousgeometrical isomers, i.e., compounds having the same carbon skeleton butoccurring in various cisand transforms, and, in the case of glycolshaving the hydroxymethyl groups in the 2- or 3- positions, occurring insynand anti-forms as well. It has been found that the glycol mixturesobtained in this way can be purified readily to eliminate traces ofesters and other non-glycol impurities by conventional purificationprocedures such as recrystallization or distillation, and that theglycol products obtained in this form have excellent utility in thepreparation of polyesters without separating the isomers unless it is sodesired.

Examples of the novel glycols of the present invention are shown inTable I, together with the starting material acids from which they maybe derived by the twostage reduction process described above.

TABLE 1.-BIS(CARBOXYPEHNOL) COMPOUNDS AND GLYCOLS OBTAINED BY THEREDUCTION THEREOF Acid Alycol 1 4,4-bibenzic acidBifiG-hydroxymethylcyeloexy 2 3,3'-bibcnzoic acidBis(3-hgdroxymethyicycloexy 3 3,4-bibenzoic acid 3,4Bis(hydroxymethyl)-I bieyclohexyl) 4 2,2'-dimethyl-4,4'-bibenz0ieBis(4-hydroxymethyl-Z-methylacid. cyclohexy l) 53,3-dimethyl-4,4bihenzoio Bis(4 hydroxymethyl-3- acid. methyleyclohexyl) 6 2,2-dimethyl-5,5- bibenzoic Bist3-hydroxymethyl-6- acid.methylcyclohexyl) 7 2,2-di-isopropyl-5-5-biben Bis(3-hydroxymethyl-6-zoie acisopropylcyclohexyl). 8 Bis(4-carboxyphenyl)-Bis(4-hydroxymethylcyc10- methane. hexyDmethane. 9 Bis(3-earboxyphenyl)-Bis(3-hydroxymethylcyclomethane. hexyDmethane. 10. 1,1-bis(4-carboxy-1,1-bis(4-hydroxyrnethylphenyDethane. cyclohexyDethane. 11..1,2-bist4-carboxyphenyl) 1 ,2-bis(4'hydroxymethanylethane.cyclohexyDeth-ane. 12 1,2-bis(3earboxyphenyl)1,2-bis(3-hydroxymethylcycloethane. hexyDethane. 132,2-bis(4-carboxyphenyl) 2,2-bis(4-hydroxymethylpropane.eyelohexyhpropane. 14 1,3bis(4-carboxyphenyl)-1,3-bis(4-hydroxymethylpropane. cyclohexyhpropane. 15.". 1,4-bis(4carboxyphenyl) 1,4-bis(4-hydroxymethy1 butane. eyclohexyDbutane. 16-1,1-bis(4-carboxyphenyl) 1,1-bis(4-hydroxymethylbutane.oyclohexyDbutane. 17 1,1-bis(B-carbcxyphenyl)1,1-bis(3-hydroxymethylbutane. cyclohexyDbutane. 181,2-dimethyl-1,2bis(4-car- 1,2-dimethyl-1,2-bis(4-hydroxyboxyphenyhbutane. methylcyclohexyl)butane. 19 3,3bis(3-carboxyphenyl)-3,3bis(B-hydrmrymethyh pentane. cyelohexybpentane. 203,4-dimethyl-3,4-bis- 3,4-dimethyl-3J,4-bis(4- (4-09.11)oxyphenyDhexane.hydroxy-methylcyclohexyD- hexane. 21 4,4"-p-terphenic acid1,4-bis(4-hydroxymethyleyclohexybcyclohexane. 22 4,4"-m-terphenic acid1,3-bis(4-hydroxymethyl.

cyelohexyl) cyclohex ane. 23 Bis(4-earboxyphenyl)etherBis(4-hydr0xymethylcycloheyDether. 24 Bis(4-carboxyphenoxy)-Bis(4-hydroxymethylcycloet ane. hexyloxy)ethane. 25Bis(4-carboxyphenoxy)- Bis(4hydroxymethylcyclobutane. hexyloxy)butane.26 2,8-dibenzofuraudicarboxylic 2,8bis(hydroxymethyl)dodecaachydrodibenzoiuran. 27 Diphenic acid Bis(2-hydroxyrnethylcyclohexyl). 28-2,3-bibenzoic acid 2,3-bis(hydroxymethyl)- bicyclohexyl. 292,4'-bibenzoic acid 2,4-bis(hydroxymethyl)- bicyclohexyl. 30 3,=idimethyl-2,2-bibenzoie 3,4'-dimethyl-bis(2-hydroxyaci methylcyclohexyl).31 4,4-dimethyl-2,2-bibenzoic Bis(2-hydroxyrnethyl-4- acimethylcyclohexyl). 32 5,5-dimethyl-2,2-bibenzoic Bis(2-hydroxymethyl-5-acid. methylcyclohexyl) 3,3-dimethyoxy-4,4- Bls(4-hydroiryrnethyl-3-methoxy-cyclohexyl) Bis(2-hydroxymethyl-5- methoxycycloh exyl).

bibenzoie acid. 5,5 -dimethyoxy-2,2

bibenzoic acid.

. 6ethyl-2,2"biben2oic acid B-ethyl-bis(2-hydroxymethylcyeloexyl).4-isopropyl-3-methyl- 4-isopropyl-3methyl-b1s(2- 2,2bibenzoic acid.hydroxymethylcyclohexyl) 37 2,2'-diphenylmethane-di-Bis(2-hydroxymethylcyclodicarboxylic acid. hexyD-methane.

38". 2,4'-diphenylmethane-di- 2,4-bis(hydroxymethylcyclocarboxylic acid.hexyDmethane.

39 4,4-dimethoxy-3,3-di- Bis(3-hydroxymethyl-4-phenylrnethanedicarmethoxy-cyclohexyl) boxylic acid. mehtane.

40 1,2-bis(2-carboxvphenyl)- 1,2-b1s(2-hydroxymethylethane. cyclohexyl)ethane.

41 1 ,2-13is(2-earboxy-6-methyl- 1,2-b1s (2-hydroxymethyl-6- phenyl)ethane. methylcyclohexyl) ethane.

42- 2,2 bis(2-carboxy-phenyl)- 2,2-bis(2-hydroxymethy1- butane.cyclohexyl) butane.

Although the glycol products obtained from the twostage reductionsequence can be employed directly in the preparation of polyesters, ithas been found that specific geometrical isomers can be prepared andalso that an isomerization step can be provided to alter the ratio ofthe various isomers contained in the product. In the case ofbis(4-hydroxymethylcyclohexyl), for example, it has been found thathydrogenation of dimethyl 4,4'-bibenzoate yields a mixture of threeisomeric dimethyl dodecahydro-4,4-bibenzoates. Recrystallization of theisomeric ester mixture from 90% methanol/10% HO CH Cis,ci s-bis(4-113;droxymethylcyclohexyl) wherein the carbon atoms in the l, 1', 4,and 4' positions as well as the hydrogen atoms attached to thesepositions and the carbon atoms of the hydroxymethyl groups lie in theplane of the paper, the 2, 2', 3, and 3 carbon atoms are situated abovethe plane of the paper, the 5, 5', 6, and 6' carbon atoms are situatedbelow the plane of the paper, and the symbol .9 indicates that the ringis saturated (i.e., that the 6-membered ring is a cyclohexane ring).

As described above, hydrogenation of dimethyl 4,4'-bibenzoate to amixture of dimethyl dodecahydro-4,4-bibenzoates followed byrecrystallization results in separation of quantities of one of the pureisomers (M.P. C.). Saponification of the esters remaining in the motherliquor to the sodium salts of the mixed acids yields a solution fromwhich part of the remaining product can be salted out as a relativelypure isomer. The saltedout product, when esterified with methanol,yields a geometrical isomer of dimethyl dodecahydro-4,4-bibenzoatemelting at 116 C., differing from the isomeric ester melting at 98 C.described above. Reduction of the ester melting at 116 C. with lithiumaluminum hydride produces a pure geometrical isomer of the glycol,designated herein as t,t-bis( l-hydroxymethylcyciohexyl), which has amelting point of 184 C. and yields a dibenzoate ester having a meltingpoint of 127 C. This isomer is illustrated by the following structuralformula in which each of the hydroxymethyl groups is trans to the bondconnecting the two cyclohexane rings:

HOCH2 0 Hz 0 H Transtransbis -hydroxym ethyl cycloliexyl) wherein eachof the symbols is employed as previously defined.

From the residual liquid remaining after the salting out proceduredescribed above in working up the mixture ofdodecahydro-4,4'-bibenzoates is obtained a mixed acid which, whenrecrystallized from aqueous acetic acid and estcrified with methanol,yields the third isomer of dimethyl dodecahydro-4,4'-bibenzoate in 80%purity.

Reduction of this ester with lithium aluminum hydride, followed byrepeated recrystallizations from aqueous ethanol and then from ethylacetate, produces a pure geometrical isomer of the glycol, designatedherein as c,tbis(4-hydroxymethylcyclohexyl), which has a melting pointof C. and yields a dibenzoate ester having a melting point of 76 C. Thisisomer is illustrated by the following structural formula in which oneof the hydroxymethyl groups is cis to the bond connecting the twocyclohexane rings and the other is trans:

It has been found that the preparation of the t,t-bis-(4-hydroxymethylcyclohexyl) isomer is greatly facilitated by saponifyingthe crude hydrogenation product comprising the three isomeric dimethyldodecahydro-4,4'-bibenzoates to the corresponding mixture of isomericacids, followed by heating the mixed acids at 300 C. in vacuum. Theacids are isomerized substantially completely to the isomer of the acidmost stable to heat; and upon esterification of the acid and reductionwith lithium aluminum hydride it is found that the t,t-isomer of theglycol is obtained. By this process high yields are obtained in thecoversion of the 4,4'-bibenzoate starting material tot,tbis-(4-hydroxymethylcyclohexyl) Similarly, other mixtures ofalicyclic acid isomers obtained as intermediates in the preparation ofthe novel glycols of the invention may be isomerized with aid of heat tothe most stable isomer, normally the trans, transisomer, as a step inthe production in high yield of the corresponding pure geometricalisomer of the glycol. For instance, dodecahydro 1,2bis(4-carboxphenyl)ethane may be heated to 300 C. in vacuum, followed byesterification of the acid and reduction with lithium aluminum hydride,to form a pure geometrical isomer of the corresponding glycol,designated herein as t,t-1,2-bis(4-hydroxymethylcyclohexyl)ethane, whichhas a melting point of 167 C. and forms a dibenzoate ester having amelting point of 109 C. This isomer is illustrated by the followingstructural formula:

The novel polymers of the invention, in its broadest scope, comprisesolid linear condensation polymers of a dicarboxylic acid and a glycolcontaining two hydroxymethylcyclohexyl groups, any additionalconstituents of the glycol being selected from the class consisting ofether oxygen and saturated hydrocarbon groups having a total of up to 8carbon atoms. More specifically, the polymer may be composed of adicarboxylic acid and at least one bifunctional compound reactive withdicarboxylic acids to form linear condensation polymers, at least 50 molpercent of said bifunctional compound consisting of said glycolcontaining two hydroxymethylcyclohexyl groups. The remainder of thebifunctional component may be another dihydroxy compound, a diamine, ahydroxyacid, a hydroxyamine, or an aminoacid. When more than onebifunctional component is reacted with the dicarboxylic acid, theresulting interpolymer may be either random or segmented (block)interpolymer. The dicarboxylic acid, which may contain up to about 26carbon atoms, preferably contains at least one 6-membered carbocyclicnucleus and the shortest chain of carbon atoms connecting the twocarboxyl groups preferably includes at least three cyclic carbon atomsof the nucleus.

A preferred embodiment of the invention comprises polyesterscharacterized by possessing recurring units of the following formula:

in which n is O or 1, A is a divalent organic radical corresponding tothe radical A in the starting material dicarboxylic acid, A(COOH) andthe other symbols are employed as previously defined. Preferably, Acontains from 6 to 24 carbon atoms including at least one 6-mernberedcarbocyclic nucleus, and the carboxyl groups are separated by a chain ofat least three nuclear carbon atoms. Thus, A may be an arylene,aralkylene, or cycloalkylene radical of 6 to 24 carbon atoms derivedfrom the dicarboxylic acid of the formula A(COOH) the carboxyl groupsbeing attached in positions other than ortho positions on the ring.

The starting material dicarboxylic acids from which the polyesters areprepared may be in the form of their esterforming derivatives, i.e.,their carbonyl halides, anhydrides, salts, or esters, particularly theiresters with the lower aliphatic alcohols or with phenol. 4,4-Bibenzoicacid is an example of a dicarboxylic acid which may be used with thenovel glycols to form polyesters; and this acid is indeed particularlypreferred for the purpose of producing polyesters suitable for spinningtextile filaments. Other examples of suitable acids include 2,2'- and3,3'-dimethyl-4,4-bibenzoic acid, 2,2-dibromo-4,4'-bibenzoic acid,bis-(4-carboxyphenyl)-methane, 1,1- and 1,2 bis(4-carboxy henyl)ethane,2,2 bis(4-carboxyphenyl)propane, 1,2 bis(4-carboxyphenoxy)ethane,bis-4-carboxyphenyl ether, bis-4-carboxyphenyl sulfidebis-4-carboxyphenyl ketone, bis-4-carboxyphenyl sulfoxide, bis-4-carboxyphenyl sulfone, 2,8-dibenzofurandicarboxylic acid, terephthalicacid, methylterephthalic acid, 2,5- or 2,6-dimethylterephthalic acid,chloroterephthalic acid, 2,5-dichloroterephthalic acid,fiuoroterephthalic acid, isophthalic acid, the naphthalenedicarboxylicacids and especially the 1,4- 1,5-, 2,6-, and 2,7- isomers, oxalic acid,phenylenediacetic acid, 4-car boxyphenoxyacetic acid, mand pterphenyl4,4"-dicarboxylic acid, dodecahydrobi benzoic acid, 1,1bis(4-carboxyphenyl)cyclohexane, hexahydroterephthalic acid,4,4-stilbenedicarboxylic acid, andoctadecahydro-m-terphenyl-4,4"-dicarboxylic acid. The divalent A radicalis preferably composed primarily of carbon and hydrogen but may contain,in addition to the two carboxyl groups, other non-hydrocarbon components or substituents which are inert in the polyesterificationreaction. For example, halogen substituents may be present. The radicalA may also be a chalkogen-containing radical wherein each chalkogen atomis bonded to carbon or a different chalkogen atom, and no carbon isbonded to more than one chalkogen atom. Thus, the repeating units maycontain ether, carbonyl, sulfide, sulfoxide, or sulfonyl radicals.Mixtures of the dicarboxylic acids may be employed.

The polyesters of the invention are prepared by reacting a dicarboxylicacid or an ester-forming derivative thereof, as described above, withone of the novel cycloalkylene glycols of the invention, i.e.,bis(hydroxymethyl cyclohexyl) or a bis(hydroxymethylcyclohexyl)alkane orether, or an ester-forming derivative of the desired glycol. By anester-forming derivative of the glycol is meant a derivative of thenovel glycol containing functional groups equivalent to the hydroxylgroups in their ability to react with carboxl groups, such as esters ofthe glycol with acetic acid or other lower aliphatic acids.

A convenient method for preparing the polymers involves reaction of analkyl ester of a dicarboxylic acid with one of the novel cycloalkyleneglycols in an ester interchange reaction followed by polycondensation athigh temperature and at low partial pressure of the glycol, until apolymer of the desired molecular weight is produced. In carrying out theester interchange reaction, at least one molecular proportion of thenovel cycloalkylene glycol per molecular proportion of the dicarboxylicester should be used, preferably about 1.5 to 1.8 mols of the glycol permol of the ester. It is desirable to employ an ester of the dicarboxylicacid formed from an alcohol or a phenol with a boiling pointconsiderably below that of the novel cycloalkylene glycol so that theformer can be removed easily from the reaction zone by distillation. Itis preferred to use the methyl or ethyl esters, as these esters areformed from alcohols which, because of their relatively low boilingpoints, are easily separated by distillation from the glycol. Heatingshould be above the melting point of the reaction mixture and above theboiling point of the alcohol or phenol to be displaced. Heating shouldbe elfected under conditions such that the displaced alcohol or phenolcan be removed from the reaction zone, usually by means of conventionaldistillation equipment. The heating is usually at atmospheric pressure,but higher or lower pressures may be used if desired. The esterinterchange reaction is advantageously carried out in the presence ofester interchange catalysts such as manganous acetate, calcium acetate,litharge, sodium methoxide, sodium hydrogen hexabutoxytitanate,tetra-alkyl titanates such as tetraisopropyl titanate, or other suitableester interchange catalysts as described in the literature relating topreparation of polyesters.

Following the ester interchange reaction, heating is continued underreduced pressure until the excess glycol is removed and thepolymerization reaction has proceeded to the desired degree. The finalstages of polymerization may be carried out with polymer in the moltenstate or, if desired, the reaction may be completed by solid phasepolymerization. The polymerization reaction may be carried out in thepresence of catalysts such as antimony trioxide, litharge, zinc acetate,or other suitable polycondensation catalysts as described in theliterature. Sodium hydrogen hexabutoxytitanate and the tetra-alkyltitanates such as tetraisopropyl titanate are examples of catalystswhich may be used for both the ester interchange and polymerizationsteps.

As used herein the term polyester is intended to include not onlyhomopolyesters but also copolyesters, terpolyesters, and the like.

While the preferred embodiment of the invention comprises polyesters inwhich all, or substantially all (i.e., greater than 90%), of therecurring structural units consist of esters of dicarboxylic acids witha bis(hydroxymethylcyclohexyl) or a bis(hydroxymethylcyclohexyl) alkane,or ether, particularly with bis(4-hydroxymethylcyclohexyl) or abis(4-hydroxymethylcyclohexyl)alkane, it is to be understood that theinvention also comprises polyesters in which residues of other hydroxycompounds are present. In general, at least about 50 mol percent of thehdroxy component of the polyester should be a bis-(hydroxymethylcyclohexyl) a bis(hydroxymethylcyclohexyl) alkane, ormixtures thereof, although of course smaller proportions can beemployed. By hydroxy component of the polyester is meant the sum of allthe hydroxy-substituted compounds which would be formed by hydrolysis ofthe carbonyloxy linkages in the polymer chain. The remainder of thehydroxy component of the polyester, up to about 50 mol percent, may beany suitable dihydroxy compound of hydroxycarboxylic acid. Examples ofsuch compounds include ethylene glycol, propylene glycol, butyleneglycol, 2,2-dimethylpropylene glycol, 2methyl- 2-ethylpropylene glycol,2 methyl 2 propylpropylene glycol,2,2,3,3,4,4-hexafiuor-1,5-pentanediol, hexamethylene glycol,decamethylene glycol, diethylene glycol, ethylene thiodiglycol, cis ortrans-hexahydro-p-xylylene glycol, cisor trans-quinitol, decahydro-l,4-,-l,5-, -2,6-, or -2,7-bis(hydroxymethyl)naphthalene,l,1-bis(hydroxymethyl)cyclohexane, 4-(2 hydroxyethyl)benzoic acid, and4-(2-hydroxyethoxy)benzoic acid.

The remainder of the hydroxy component may also be a dihydric phenol. Aconvenient method of preparing such copolyesters involves (A)preparation of a homopolyester of one of the novel cycloalkylene glycolsof the invention and a dicarboxylic acid as described above, (B)preparation of a homopolyester of the dihydric phenol with thedicarboxylic acid, e.g. by reacting the dihydric phenol with thediphenyl ester of the acid in the presence of sodium acetate as acatalyst, and (C) melt blending the glycol polyester and the dihydricphenol polyester in the desired proportions under an atmosphere ofnitrogen. The blended mixture initially forms a block copolyester, butif the mixture is held an hour or so in the melt the copolyester becomesrandom. The catalysts present in the homopolyester also serve ascatalysts for the randomization of the copolyester. Suitable dihydricphenols for the preparation of such copolyesters include hydroquinone,resorcinol, 4,4'-dihydroxybiphenyl, 3,3- dibromo-4,4-dihydroxybiphenyl,bis(4 hydroxyphenyl) methane, 2,2-bis(4-hydroxyphenyl)propane,2,2-bis(3,5- dichloro-4 hydroxyphenyl)propane, bis(4hydroxyphenyl)ether, bis(4-hydroxyphenyl) sulfone, bis(4-hydroxyphenyl) ketone, andbis(4-hydroxyphenyl) sulfoxide.

Hydrocarbons substituted with two hydroxy groups, or substituted withone hydroxy group and one carboxylic acid group, are normally preferredas copolymeric hydroxy components; however, halogen or chalkogensubstituents or radicals may also be present, as described above withrespect to the dicarboxylic acid. A minor amount of a dicarboxylic acidor a hydroxy component carrying a metallic sulfonate salt, carboxylatesalt, phosphonate salt, or the like may also be present.

Polyesteramides may be formed in accordance with the present inventionfrom a dicarboxylic acid and a mixture of bifunctional compoundsincluding at least one diamine or aminocarboxylic acid, at least 50 molpercent of said mixture of bifunctional compounds comprising the novelglycol containing two hydroxymethylcyclohexyl groups as defined above.Since more than two monomeric ingredients are involved in thepreparation of the polyesteramides, variations in the preparation ofthese interpolymers will be apparent. For example, instead ofpolymerizing a mixture of the various monomers, a mol of a diamine maybe pre-reacted with two mols of a halt ester, half acid chloride ofdicarboxylic acid and the resulting amide-diester may be reacted, withor without the addition of another diester, with the novel glycol.Preferred bifunctional compounds in which at least one of the functionalgroups is an amine group are those in which the amine group is attachedto a saturated carbon atom. Suitable examples includehexamethylenediamine, ethylenediamine, bis(4 aminocyclohexyl)methane,p-xylylenediamine, 3-amino-2,2-diphenylpropanol, hydroxyethylamine,-aminocaproic acid, and p-aminomethylbenzoic acid.

Either copolyesters or polyesteramides may be prepared in segmented formrather than in random form in accordance with the present invention.Such block polymers are suitably prepared by melt blending a polyesterof a dicarboxylic acid and the novel glycol containing twohydroxymethylcyclohexyl groups with a separately prepared secondpolyester, or with a separately prepared polyamide, until aninterpolyrner is formed; and then cooling the segmented interpolymerbefore the order of the recurring structural units becomes substantiallyrandom through further ester interchange or ester-amide interchangereactions.

The melt stability of the segmented interpolymer is greatly enhanced byselecting the polymers to be melt blended such that at least one of themundergoes such interchange reactions only quite slowly. Polyestersderived from a sterically hindered glycol or acid, such as2,5-dimethylterephthalic acid, 2,2 dimethyl-1,3-propanediol,2,2,5,5,-tetramethyladipic acid, 2,2,5,5,-tetramethylhexamethyleneglycol or 2,2,4,4-tetramethyl-1,3-cyc1obutylene glycol, have therequired low rate of interchange reactivity to form melt-stablesegmented interpolymers with other polyesters or with polyamides.

Within the broad range of useful polymers, including lower meltingpolyesters suitable for molding compositions, it is generally consideredthat those polyesters melting above about 200 C. and as high as about325 C. are especially advantageous for extrusion in unmodified form toproduce fibers and films. Many of the novel polyesters of this inventionare even higher melting and are especially adapted for high temperatureapplications, e.g., for use in electrical tapes and in the manufactureof insulators for electric motors, etc. Extrusion or shaping of thehigher melting polyesters is generally facilitated by the use ofplasticizers, especially by plasticizers such as 1,2- diphenoxyethane orptoluenesulfonamide which may be removed from the shaped polyesterarticle by leaching with water or other solvent, or by heating at atemperature suflicient to drive off the plasticizer. Polyesters havingan intrinsic viscosity of at least about 0.2 are considered to be ofsufiiciently high molecular weight for utility in forming moldedarticles as well as films. For use in extruding fibers and filaments,polycondensation is usually continued until the intrinsic viscosity isat least about 0.3.

The following examples will serve to describe the preparation ofbis(4-hydroxymethylcyclohexyl) and other bis-(4-hydroxymethylcyclohexyl)alkanes, including separation of certain ofthe pure geometrical isomers and selective methods for preparing certainspecific geometrical isomers, as well as typical polymers and copolymersderived therefrom. The examples are not intended to be limitative.

As used herein, the polymer-melt temperature, abbreviated PMT, isdefined as that temperature where a polymer sample becomes molten andleaves a trail when moved across a hot metal surface with moderatepressure. Practical considerations in PMT determinations are discussedby Sorenson and Campbell in Preparative Methods of Polymer Chemistry,Interscience Publishers, Inc., N.Y., pages 49-50 (1961).

EXAMPLE 1 Preparation of bis(hydroxymethylcyclohexyl) isomers (A)Hydrogenation of dimethyl 4,4'-bibenzoate.-To a solution of 30 g. ofdimethyl 4,4'-bibenzoate in 150 cc. of acetic acid is added 0.5 g. offinely-divided platinum oxide (Adams Catalyst), after which the mixtureis bydrogenated on a Parr shaker for 6 hours at 45 C. under anatmosphere of 50 psi. of hydrogen. The catalyst is then filtered off andthe acetic acid is neutralized by adding aqueous sodium carbonate. Theproduct is dimethyl dodecahydro-4,4-bibenzoate, a solid of low meltingpoint.

(B) Alternative hydrogenation prcedures.-Hydrogenation of dimethyl4,4'-bibenzoate in dioxane solution is carried out as in part A, exceptthat ruthenium oxide is substituted for the platinum oxide and highpressure apparatus is used (hydrogen at 5000 psi). A low melting esterproduct, dimethyl dodecahydro-4,4'-bibenzoate, is obtained.

Similarly, dipotassium 4,4-bibenzoate may be hydrogenated in aqueoussolution at 5000 p.s.i. to form di potassiumdodecahydro-4,4'-bibenzoate; or an aqueous slurry of bibenzoic acid maybe hydrogenated to form dodecahydrobibenzoic acid.

(C) T rans,trnns dimethyl dodeca'hydro 4,4'-bibenzoate-Ninety g. ofdimethyl dodecahydro-4,4'-bibenzoate, prepared as described in part A,is dissolved in 500 cc. of methanol and 200 cc. of water. To thesolution is added 80 g. of sodium hydroxide, after which the solution isrefluxed overnight. The reaction mixture is worked up by distilling offthe methanol and acidifying the aqueous solution with concentratedhydrochloric acid. The solid so obtained, dodecahydro-4,4'-bibenzoicacid, is washed and dried, the yield being 84 g. The acid melts over awide range, 220-350 C.

The acid is isomerized by placing it in a container under a vacuum ofmm. of mercury and heating it for one hour at 250 C., then for two hoursat 300 C. The resulting product has a melting point of 355 C.

A solution of 84 g. of the isomerized acid in 800 cc. of methanol isrefluxed overnight with cc. of concentrated sulfuric acid and poured onice, after which the product is filtered otf and washed. After tworecrystallizations from a mixture of 90 parts of methanol and 10 partsof water, the product melts at 116 C. Gas liquid chromatography of asample (4 ft. column of high molecular weight polyethylene glycol wax at250 C.) establishes that all of the material passes through in a singlepeak, indicating that the product is the pure geometrical isomer,trans,trans-dimethyl dodecahydro-4,4-bibenzoate (ref.: Fichter andHolbro, Helv. Chim. Acta 21, 141, 1938).

(D) Identification of isomeric esters. The ester obtained by the highpressure hydrogenation procedure of part B is subjected to gas liquidchromatography. Three peaks are observed, amounting to 60%, 35%, and 5%of the product, respectively. When pure trans,trans-dimethyldodecahydro-4,4-bibenzoate, prepared as described in part C, is added tothe sample and another gas liquid chromatography determination is made,the third peak is enhanced. A sample of the ester product from part B isthen heated for twenty-four hours with sodium methoxide in refluxingmethanol. Gas liquid chromatography of the resulting ester indicatesthat the isomer composition has been greatly changed; the first, second,and third peaks amounting to 5%, 35% and 60%, respectively. Based onthis data, the order of appearance of the peaks corresponds to thecis,cis-, cis,trans-, and trans,trans-isomers, respectively; and theesters are correspondingly designated hereinbelow as the c,c-, c,tandt,t-isomers, respectively.

The ester product of part A is subjected to gas liquid chromatographyand it is determined that the isomers composition is 45% c,c-, 45% c,t-,and 10% t,t-, based on the above designation.

(E) c,c-dimethyl dodeeahydro-4,4'-bibenz0ate. A sample of dimethyldodecahydro-4,4-bibenzoate prepared by high pressure hydrogenation asdescribed in part B is recrystallized from an approximately 10% solutionin a mixture of parts of methanol and 10 parts of water. As determinedby gas liquid chromatography, the resulting crystals correspond to apure sample of c,cdimethyl dodecahydro-4,4'-bibenzoate as designated inpart D above. The melting point of the ester is 98C.

(F) c,t dimethyl doziecahydro 4,4'-bibenz0ate. The mother liquorremaining after separation of the c,c-isomeric ester in the procedure ofpart E is analyzed by gas liquid chromatography, and it is found thatthe ratio of isomers remaining in it is 20% c,c-, 65% c,t-, and 15%t,t-. Sodium hydroxide is added to the solution and the mixture isrefluxed overnight. Sodium chloride is added to the solution and theresulting precipitate (sodium salt of the t,t-isomer of the acid) isfiltered off. The remaining acid obatined upon acidification isrecrystallized from aqueous acetic acid and the product is thenesterified by refluxing overnight in methanol in the presence ofconcentrated sulfuric acid. The crystals obtained upon recrystallizationfrom solution in 90 parts of methanol and 10 parts of water melt at 56C. Gas liquid chromatography indicates that it comprises c,tdimethyldodecahydro-4-4-bibenzoate of 80% purity.

(G) Reduction of dimethyl dodecahydro-4,4-bibenzoate.Fifty-one g. ofdimethyl dodecahydro-4,4-bibenzoate, prepared as described in part A, isdissolved in 500 cc. of ether and the solution is added dropwise to arefluxing slurry of 20 g. of lithium aluminum hydride in 500 cc. ofether. After the addition is complete, the mixture is refluxed for 24hours. Excess hydride is then destroyed with 100 cc. of ethyl acetateadded drop by drop. The mixture is cooled to -20 C. and 75 cc. ofconcentrated sulfuric acid is diluted with 200 cc. of Water and addeddropwise. After allowing the mixture to warm to room temperature, enoughwater is added to give a sludge and an easily decanted ether layer. Theaqueous layer is extracted with ether and the combined ether extractsare evaporated, after which the resulting glycol is recrystallized fromaqueous ethanol. The product, bis (4-hydroxymethylcyclohexyl), has amelting point of 100ll7 C.

(H) Geometrical isomers of bis(4-hydr0xymethylcyclohexyl). The procedureof part G is repeated for each of the c,c-, c,t-, and t,t-isomers ofdimethyl dodecahydro-4,4'-bibenzoates prepared as described in parts E,F and C, respectively. The resulting glycols are given the samedesignation with respect to structure of the geometrical isomer as thecorresponding dimethyl esters. The c,t-bis(4-hydroxymethylcyclohexyl)product is recrystallized from aqueous ethanol and then from ethylacetate until a constant melting point, C., is

M.P. of Isorners C.)

ccm ctm Dimethyl HBB 98 1 56 116 Glycol 123 135 184 Glycol dibenzoate113 76 127 Phenylurethane 174 145 230 1 80% pure.

(I) Hydrogenation procedure for reduction of dimethylda'ecahydro-4,4-bibenz0ate. In a stirred autoclave is placed a mixtureof 1 part by weight of dimethyl dodecahydro-4,4-bibenzoate having anisomer distribution of about 55% c,c, 40% c,t, and 5% t,t; 3.5 parts byweight of cyclohexanol as a solvent; and 0.1 part by weight of copperchromite catalyst. The autoclave is closed, the contents are stirred andbrought to a temperature of 260 C., and the autoclave is pressurizedwith hydrogen at 4500 p.s.i.g. for 30 minutes. The contents of theautoclave are cooled, filtered to remove the catalyst, and the solventis removed by distillation at about 120 mm. of mercury. The pressure isthen lowered to about 1 mm. and a low boiling foreshot of unreactedester is taken until the temperature of the overhead vapors reachesabout 175 C. The still residue is cooled and purified by crystallizationfrom about 8 times its wtight of toluene. The solid is filtered from theslurry at about 30- 35 C., and the product is air dried. The resultingbis(4- hydroxymethylcyclohexyl) melts below 100 C. and is found to beentirely free of carbomethoxy groups and to contain isomers in theapproximate distribution of 54% c,c, 39% c,t, and 7% t,t.

Higher temperatures, higher catalyst ratios, lower hydrogen pressuresand longer reaction times than exemplified are conditions which favor achange in the isomer distribution, generally with an increase in theamount of t,t isomer in the glycol product.

(.1) Preparation of bis(3-hydroxymethylcyclohexyl). Dimethyl3,3'-bibenzoate is hydrogenated in accordance with the general procedureof part A above to produce a mixture of geometrical isomers of dimethyldodecahydro-3,3'-bibenzoate. When the ester is subjected to gas liquidchromatography, four peaks are observed, amounting to 3%, 2%, 32%, and63% of the product in order of appearance of the peaks. The predominantisomer, isolated as the acid by saponification and recrystallizationfrom acetic acid, has a melting point of 264 C. The pure dimethyl esterof the predominant isomer, formed by re-esterification of the pure acid,has a melting point of 59 C. Reduction of the pure ester with lithiumaluminurn hydroxide in accordance with the general procedure of part Gabove produces a pure isomer of bis(3- hydroxymethylcyclohexyl) having amelting point of 138 C. and identified as the c, syn, cisomer.

(K) Preparation. of bis(Z-hydroxymethylcyclohexyl).- Dimethyl diphenateis hydrogenated in accordance with the general procedure of part A aboveto produce a mixture of geometrical isomers of dimethyldodecahydrodiphenate, as shown by the appearance of four major peaks andtwo minor peaks when the ester mixture is subjected to gas liquidchromatography. The esters are equilibrated by heating the mixture fortwenty-four hours with sodium methoxide in refluxing methanol, afterwhich the equilibrated mixture of esters is reduced with lithiumaluminum hydride in accordance with the general procedure of part Gabove. The product, a liquid mixture 12 of isomers ofbis(2-hydroxymethylcyclohexyl), is purifled by distillation.

EXAMPLE 2 Preparation of bis(4-hydroxymethylcyclohexyl)ethane isomersThe procedure of part A of Example 1 is repeated, substituting1,2-bis(4-carbomethoxyphenyl)ethane for dimethyl 4,4'-bibenzoate andcarrying out the hydrogenation at 40 C. to produce a mixture ofgeometrical isomers of l,2-bis(4-carbomethoxycyclohexyl)ethane.

The mixture of isomeric esters is recrystallized from methanol to obtaina pure geometrical isomer. Based on a gas liquid chromatographydetermination, the recrystallized product is designed as the c,c-isomerof the ester. The ester is then reduced with lithium aluminum hydride inaccordance with the general procedure of part G of Example 1 to form theglycol, c,c-l,2-bis (4-hydroxymethylcyclohexyl)ethane.

Reduction of the mixture of isomeric esters with lithium aluminumhydride correspondingly yields a mixture of three geometrical isomers ofthe glycol identified as c,c-, c,t-, and t,t-,1,2-bis(4-hydroxymethylcyclohexyl)ethane on the basis of gas liquidchromatography determination.

A portion of the mixture of isomeric esters is also saponified to theacid, heated, and re-esterified to the dimethyl ester in accordance withthe general procedure of part C of Example 1. The resultingt,t-1,2-bis(4- carbomethoxycyclohexyl)ethane is then reduced withlithium aluminum hydride to form the glycol, t,t-1,2-bis(4-hydroxymcthylcyclohexyl ethane.

Listed below are the melting points of the 1,2-bis(4-carbomethoxycyclohexyl)ethanes (dimethyl HB2B) together with the meltingpoints of the respective glycols as well as their dibenzoate andphenylurethane derivatives:

M.P. of Isomers C.)

Preparation of Other Glycols (A) Bis(4-Izydr0xymethylcyclohexyl)methane.l3is(4- carbornethoxyphenyl)methane is hydrogenated inaccordance with the general procedure of part A, Example 1, to produce amixture of geometrical isomers of bis(4- carbomcthoxycyclohexyl)methanewhich is then saponificd to the acid, heated, and re-esterified to thedimethyl ester by the method of part C of Example 1. On the basis of agas liquid chromatography determination, the product is identified as amixture of of the t,tisomer and 15% of the c-t-isomer. The predominantlyt,t-ester is reduced with lithium aluminum hydride in accordance withthe general procedure of part G of Example 1 to form the glycol,bis(4-hydroxymethylcyclohexyl)methane, M.P. 144 C. after repeatedrecrystallization from methanol-water. The dibenzoate derivative of theglycol metlts at 124 C. and the phenylurethane derivative at 168 C.

A portion of the initial hydrogenated mixture of esters isrecrystallized from methanol to obtain another pure geometrical isomer.Based on a gas liquid chromatography determination, the recrystallizedproduct is designated as c,c-bis(4-carbomethoxycyclohexyl)methane, M.P.63 C. Reduction of this ester with lithium aluminum hydride yieldsc,c-bis(4-hydroxymethlcyclohexyl) methane, M.P. 86 C. The dibenzoate ofthe glycol melts at 85 C.

(B) 2,2 bis(4 hydroxymethylcyclohexyl)pr0pane.-- 2,2-bis(4-carbomethoxyphenyl) propane is hydrogenated by the method of part Aof Example 1 to produce a mixture of geometrical isomers of2,2-bis(4-carbomethoxycyclohexyl)propane which is then saponified to theacid, heated, and re-esterified in the manner of part C of Example 1 toform t,t-2,2-bis(4-carbomethoxycyclohexyl) propane, M.P. 105 C. Lithiumaluminum hydride reduction of the t,t-ester yieldst,t-2,2-bis(4-hydroxymethy1- cyclohexyl)propane, M.P. 122 C. Thedibenzoate derivative of the glycol melts at 125 C. and thephenylurethane derivative at 154 C.

Recrystallization of a portion of the initial hydrogenated mixture ofesters yields "c,c-2,2-bis(4-carbomethoxycyclohexyDpropane, M.P. 98 C.Reduction of the ester yields c,c 2,2 bis(4 hydroxymethylcyclohexyl)propane, M.P. 165 C. The dibenzoate of the glycol melts at 153 C.

(C) 1,3 bis(4 hydroxymethylcyclohexyl)prpane. The experiment of thefirst paragraph of part B of this example is repeated, substitutingl,3-bis(4-carbomethoxyphenyDpropane as the starting material in place ofits 2,2- isorner. The glycol product ist,t-1,3-bis(4-hydroxymethylcyclohexyDpropane, M.P. 109. The dibenzoatederiva tive of the glycol melts at 99 C. and the phenylurethanederivative at 170 C.

(D) 2,3 dimethyl 2,3 bis(4hydroxymethylcyclohexyl)bmane.p-Isopropy1benzoic acid is coupled byheating it with di-t-butyl peroxide at 140 C., yielding bicumic acid.Diethyl bicumate is prepared by esterifying the acid in mixed ethanoland sulfuric acid, after which the ester is hydrogenated over rutheniumoxide in accordance with the general procedure of part B, Example 1. Theproduct, as shown by gas liquid chromatography, comprises a mixture ofthree geometrical isomers. Recrystallization of a portion of the productfrom methanol yields a pure isomer of diethyl dodecahydrobicumate havinga melting point of 124 C. and identified as the c,cisomer. Following thegeneral procedure of part C of Example 1, a portion of the mixture ofdiethyl dodecahydrobicumates is saponified to the mixture ofcorresponding acids, following which the acid mixture is isomerized byheating it at one hour at 300 C. The solid acid remaining afterextraction with boiling acetic acid is then esterified with mixedmethanol and sulfuric acid, yielding a pure isomer of dimethyldodecahydrobicumate having a melting point of 87 C. and identified asthe t,t-isomer. Reduction of the ester produces a pure isomer of 2,3-dirnethyl 2,3 bis(4 hydroxymethylcyclohexyl)butane having a meltingpoint of 161 C. and identified as the t,t-isomer of the glycol.

Recrystallization of the solute from the acetic acid extractionprocedure from 65% aqueous acetic acid yields another isomer ofdodecahydrobicumic acid. Esterification of this isomer in mixed methanoland sulfuric acid yields a 95% pure isomer of dimethyldodecahydrobicumate having a melting point of 50 C. and identified asthe c, -isomer. Reduction of this ester produces an isomer of 2,3dimethyl 2,3 bis(4 hydroxymethylcyclo heXyDbutane having a melting pointof 125 C. and identified as the c,t-isomer of the glycol. Reduction ofdiethyl c,c dodecahydrobicumate correspondingly yields c,c 2,3 dimethyl2,3 bis(4-hydroxymethylcyclohexyDbutane.

(E) 1,3 bis(4 hydroxymethylcyclohexyl)cyclohexane.-Dimethyl 4,4" mterphenyldicarboxylate is hydrogenated over ruthenium oxide, yielding aproduct which is a mixture of three isomers of1,3-bis(4-carbomethoxycyclohexyl)cyclohexane, as determined by gasliquid chromatography. The mixed esters are saponified to form thecorresponding mixture of acids, which is then isomerized at 250-300 C.for three hours and extracted with acetic acid. The insoluble acid isesterified with mixed methanol and sulfuric acid and the resultingester, 1,3- bis(4 carbomethoxycyclohexyl)cyclohexane, is recrystallizedfrom aqueous methanol until it is 98% pure as shown by gas liquidchromatography. The ester has a melting point of 108 C. and isidentified as the t,c,tisomer. Reduction of the ester with lithiumaluminum hydride gives 1,3 bis(4 hydroxymethylcyclohexyl)cyclohexane,having a melting point of 147 C. after three crystallizations fromxylene and identified as the t,c,tisomer of the glycol.

(F) Bis(4 hydroxymethylcyclohexyl)ether.Bis(4- carbomethoxyphenyl) etheris hydrogenated to form bis (4-carbomethoxycyclohexyl) ether by themethod of part A of Example 1. The product is saponified, extracted withaqueous acetic acid to remove the various by-products, re-esterifiedwith mixed methanol and sulfuric acid, and reduced with lithium aluminumhydride, yielding a liquid mixture of isomers ofbis(4-hydroxymethylcyclohexyl) ether, after which the mixture ispurified by distillation.

(G) 2,8 bis(hydroxymethyl)dodecahydrodibenzofuran.Dimethy12,8-dibenzofurandicarboxylate is hydrogenated in accordance with thegeneral procedure of part A of Example 1 to produce a mixture ofgeometrical isomers of dimethyl dodecahydrobibenzofuran 2,8dicarboxylate. The mixed esters are reduced with lithium aluminumhydride to form a liquid mixture of2,8-bis(hydroxymethyl)dodecahydrodibenzofuran isomers. The dibenzoatederivative of the glycol product, after trituration in heptane andrecrystallization of the insoluble dibenzoate product from ethanol, hasa melting point of 136 C.

(H) Additional glycols-The starting material esters of Table I arereduced to the corresponding dodecahydro esters in accordance with thegeneral procedure of part B of Example 1, after which lithium aluminumhydride reduction by the method of part G of Example 1 yields thecorresponding glycols listed in the table.

The various starting material esters listed are available throughprocedure previously described in the art. The alkyl substitutedbibenzoate esters are conveniently derived by the Ullmann method. Forinstance, 2,2'-dimethyl-S,5'-dicarbomethoxybiphenyl is prepared by thecoupling of methyl 3-iodo-4-methylbenzoate as described by Kenner andWithan, J. Chem. Soc. 103, 237 (1913). The corresponding2,2'-di-isopropyl derivative may be prepared similarly by diazotizationof 3-.aminocuminic acid followed by the Sandmeyer reaction andesterification to form methyl 3-iod0-4-isopropylbenzoate and subsequentcoupling by the Ullmann method.

EXAMPLE 4 Poly(bicyclohexyl-4,4-dimethylene 4,4'-bibenzoate) Into asmall polymer tube is placed 6.75 g. of dimethyl 4,4'-bibenzoate (0.025mol), 12.45 g. of bis(4-hydroxymethylcyclohexyl) (0.055 mol) prepared asdescribed in part G of Example 1 (mixed geometrical isomers), and 6drops of an 8% solution of sodium hydrogen hexabutoxytitanate inn-butanol as a catalyst. The ingredients are melted and a capillary fornitrogen flow is inserted into the polymer tube. Ester exchange iscarried out for 2.5 hours at 230 C. with evolution of methanol, afterwhich the flow of inert gas is changed from nitrogen to xylene, thetemperature is raised to 285 C., and vacuum is applied gradually untilthe pressure is reduced to 0.07 mm. of mercury. After 2.5 hours ofpolymerization at this temperature and pressure with a continuous slowstream of xylene maintained through the tube, the mixture is cooled anda white solid having an intrinsic viscosity of 0.56 is produced.

The polymeric material prepared as described above is crushed to acoarse powder and then heated for 4 hours under vacuum with a smallbleed of nitrogen at 225 C. At the conclusion of this solid phasepolymerization reaction reaction, the intrinsic viscosity of the polymeris 0.65 and the polymer-melt temperature, PMT, is 255 C.

The term intrinsic viscosity, as used herein, is defined as the limit ofthe fraction 1n(r) /c, as c approaches 0, where (r) is the relativeviscosity, and c is the concentration in grams per ml. of solution. Therelative viscosity (r) is the ratio of the viscosity of a solution ofthe I polymer in a mixture of 1 part trifluoroacetic acid and 3 partsmethylene chloride (by volume) to the viscosity of the trifiuoroaceticacid/methylene chloride mixture, per se, measured in the same units at25 C. Intrinsic viscosity is a measure of the degree of polymerization.

A molten sample of thepoly(bicyclohexyl-4,4-dirncthylene-4,4-bibenzoate) product prepared bysolid phase polymerization is extruded to form a filament, usingconventional techniques. The undrawn filament has a T of 97 C. Thefilament is oriented by drawing it around a pair of rolls between whichis situated a heating block curved on each side and maintained at 150C., using a draw ratio of 3 X. The intrinsic viscosity of the polymer inthe form of the oriented filament is measured and found to be 0.59. Theresidual elongation of the filament is 12%. The drawn filament is heattreated by boiling it in water for 15 minutes, heating it in an oven at180 C. for 3 minutes, and finally immersing it in boiling water :againfor 15 minutes. The heat-treated filament has a tenacity of 1.9 g.p.d.,and elongation of 16%, and an initial modulus of 41 g.p.d. Values fortensile strain recovery (TSR) and moduli relaxation index (MRI) are 74%and 0.05, respectively. The filament is insoluble in perchloroethyleneand is oriented and crystalline as shown by X-ray diffraction patterns.

T the second order transition temperature, is defined herein as thetemperature at which a discontinuity occurs in the curve of a firstderivative thermodynamic quantity with temperature. It is correlatedwith yield temperature and polymer fluidity and can be observed from aplot of density, specific volume, specific heat, sonic modulus or indexof refraction against temperature. A convenient method for determining Tfor a given sample of polymer is given by Pace in his U.S. Patent2,556,295 (col. 3, line 24 to col. 4, line 19).

The TSR of a filament is determined by mounting a 10-inch length of thefilament on a tensile tester with recording chart (commerciallyavailable from the Instron Engineering Corporation, Quincy, Mass.) andalso equipped with a circulating water bath which can be raised andlowered. The water bath, maintained at 40 C., is raised to immerse thefilament. After the filament has been immersed for 2 minutes withouttension it is stretched, in the Water bath, at an elongation rate of 1inch per minute. Upon reaching the desired total elongation, the sampleis held at constant length for an additional 2 minutes and the waterbath is removed. The load on the filament is then reduced to a value of0.042 g.p.d. and the filament is allowed to retract. Percent recovery iscalculated from the formula:

Units of retraction This procedure is carried out for elongations of0.5, 1, 2, and 3%, and a graph is prepared by plotting the percentrecovery against total elongation in the range O3%. TSR values areaverage percent recovery values from the range 0-3% elongation which maybe determined from the graph by usual graphical averaging procedures.

Filaments having TSR values of 60% are considered to have good tensilerecovery, while filaments exhibiting TSR values of 70% and above areconsidered quite superior.

The MRI of a filament is determined by mounting a 10-inch length of thefilament on a tensile tester of the above type, except that the testeris additionally equipped with a tube heater surrounding the filament.The filament is first heated for 4 minutes at 70 C. with the tubeheater, after which it is stretched While hot to an extension of 1%i0.05%. Upon reaching 1% elongation, the sample is held at constantlength for about 1 minute, still at 70 C., during which time the forcerequired to maintain the filament at this extension is recorded on thechart. The cross head of the tensile tester is then returned to itsoriginal position, leaving the filament with a small amount of slaclg,The circulating water bath, maintained G 9, denier percent extension G 1c denier percent extension F Fa L Fa where G is the dry modulus and G isthe wet modulus, F is the initial force required to achieve 1%elongation in the dry filament and P is the initial force required toachieve 1% elongation in the Wet filament, F is the force required tomaintain the dry filament at constant 1% elongation 45 seconds after 1%elongation is initially achieved, and L is the loss factor. Low valuesof MRI are indicative of a high predicted fabric recovery, especiallyvalues below 0.2. Comparative MRI values for commercial 66 nylon andpolyethylene terephthalate fibers are 0.9 and 0.2, respectively.

EXAMPLE 5 Copolyester fibers and films of improved dyeability with basicdyes The procedure described in Example 4 for preparation ofpoly(bicyclohexyl-4,4'-dimethylene 4,4'-bibenzoate) is repeated,substituting in place of the dimethyl 4,4'- bibenmate a mixture of0.0243 mol of dimethyl 4,4'-bibenzoate and 0.0007 mol of sodium 3,5di(carbomethoxy)benzenesulfonate. The product, poly[bicyclohexyl 4,4dimethylene 4,4'-bibenz oate/ S-(sodium sulfo isophthalate 97/3 mol percent, yields a clear, tough, drawable film which exhibits greatlyenhanced dyeability with Fuchsine SBP dye (C.I. 42,510) and other basicdyes as contrasted with a film of the corresponding homopolyester ofExample 4, which has virtually no aflinity for these basic dyes.Orientable fibers dyeable with basic dyes can be pulled from thecopolyester melt.

In the following examples, dimethyl 4, 4bibenzoate is polycondensed withvarious glycols using the same molar ratio of reactants and the samegeneral procedure for melt polymerization described in Example 4. Alsoincluded are examples of various copolyesters prepared by substituting aportion of the dimethyl 4,4-bibenzoate with the corresponding molaramount of the designated dimethyl ester.

4,4 BIBENZOATE POLYESTERS AND COPOLYESTERS PMT, Intrinsic Ex. No. GlycolEmployed C.) viscosity "c,c"-Bis(4-hydroxymethylcyciohexyl) 275 0. 6"c,t"-Bis( t'hydroxymethylcyclohexyl) 225 0. 7t,t-l3is(4-hydroxyrnethylcyclohexyl) 375 tinsel.)"c,c-BiS(4-hydroxymethylcyc10- 200 hexyDmethane. 0. 53 t-,t -B is (t-hdroxymethylcyclo- 300 0. 4

hexybmethane. 11 25%c,c"-/75%t,t"bis(4-hydroxy- 285 0. 54

methylcyclohexybmethane. 12 "c,c"-2,2-bis(4-hydroxymethylcyclo- 275 0.63

hexyl) propane. 13 t.,t"-2,2-bis(4-hydr0xymethylcyclo- 0.8

hcxyi) propane. l4 c,c"-l,2-l)is( l-hydroxyuiethylcyclu- 2.10 0.81

hcxylJethaue.

4,4 BIBENZOATE POLYESTERS AND COPOLYESTERS Intrinisc Ex. No. GlycolEmployed viscosity ate.

25 40%"c,t"-/60%t,tbis(4-hyclroxymethylcyclohexyl) copolyester from 65%dimethyl 4,4-bibenzoate/35% dimethyl dodecahydro-4,4-bibenzoate.

26 40%"c,t"-/60%t,t-"bis(4-hydroxymethylcyclohexyl); copolyester from75% dimethyl 4,4-bibenzoate/25% dimethyl 5-t-butylisophthalate.

27 40%"c,t-/60%t,t"-bis(4 hydr0xymethylcyclohexyl); copolyester from 75%dimethyl 4,4-bibcnzoate/25% 2,2-bis(4-carbomethoxycyclohexyl) propane.

1 With decomp.

(insol.)

The polymer of Example 7, when subjected to solid phase polymerizationby heating it under vacuum with a small bleed of nitrogen at 220 C. forone hour and then at 240 C. for 3 hours, has a PMT of 260 C. Undersimilar conditions, the melting point of polymer of Example 6 rises to295 C.

The polymer of Example 13, when crystallized by treating it withmethylene chloride and drying it, has a PMT of 260 C.

Drawn filaments of Example 9 have a tenacity of 0.7 g.p.d., anelongation of 10%, an initial modulus of 21 g.p.d., a TSR of 59%, and anMRI of 0.25. Corresponding values for drawn filaments of other examplesare as follows: Example 11, 0.6 g.p.d., 3.8%, 22 g.p.d., TSR of 74%, andMRI of 0.04; Example 14, 1.5 g.p.d., 11%, 4S g.p.d., TSR of 72%, and MRIof 0.17; Example 23, 0.8 g.p.d., 8.7%, and 14 g.p.d.; and Example 24,1.3 g.p.d., 9.5%, and 26 g.p.d. The fibers from Example 24 exhibit gooddyeability with 1,4-diamino-2,3-dichlor0- anthraquinone (a violetdisperse dye). Flexible films are melt pressed from the polyesters ofExamples 16 and 22. A disc of excellent toughness is molded from thepolyester of Example 14. Tough, molded discs are also prepared from thepolyesters of Examples 15, 18, 19, and 20.

In the following examples, dimethyl 4,4'-sulfonyldibenzoate ispolycondensed with various glycols in general accordance with theprocedure described in Example 4:

4,4-SULFONYLDIBENZOATE POLYESTE RS c,syn,c -Bis(Ithydroxymethylcyclehexyl) In the following examples, dimethyl terephthalate (0.03 mol) ispolycondensed with various glycol (0.06 mol) in general accordance withthe melt polymerization method of Example 4. In Example 42, acopolyester is prepared by replacing 25% of the dimethyl terephthalatewith the corresponding molar amount of dimethyl hexahydroterephthalate.

TEREPI-ITHALATE POLYESTER AND COPOLYES'IERS methylcyclohexyl);copolyester from 75% dimethyl terephthalate/ l25% dimethylhexahydroterephthaate.

The polymer of Example 31 is extruded at 265 C. to form a filament,using conventional techniques. The filament is oriented by drawing it 3Xover a C. pin. The draWn filament is oriented but amorphous as shown byX-ray diffraction patterns. The drawn filament is heat treated byboiling it in water for 15 minutes, heating it in an oven at C. for 3minutes, and finally immersing it in boiling water again for 3 minutes.The heat-treated filament is oriented and crystalline as shown by X-raydiffraction patterns. It has a tenacity of 0.9 g.p.d., an elongation of5%, and an initial modulus of 34 g.p.d. Values for TSR and MRI, asdefined in Example 4, are 71% and 0.14, respectively.

In each of the following examples, the designated dimethyl esters arepolycondensed with the designated glycols in general accordance with theprocedure described in Example 4:

METHYLENE-4,4-DIBENZOATE POLYESTERS Prepared from dimethyl methylene-Ex. 4,4-dibenzoate and the following PMI Intrinsic No. glycol- C.)viscosity 43 "t,t"-Bis(4-hydroxymethylcyclo- 0.43

hexyl).

44 t,t"-Bis(4-hydroxymethylcyclo- 240 0.70

hexyDmethane.

The poly(t,t-bicyclohexyl-4,4'-dimethylene methylene-4,4-dibenzoate) ofExample 43 is relatively amorphous when cooled from the melt; however,it can be crystallized by treating it with methylene chloride and thendrying it.

1,2FETHYLENE-4,4-DIBENZOATE POLYESTERS Prepared from dimethyl1,2-ethylcne- The poly(t,t" 1,2 ethylene bis[cyclohexyl 4- methylene]1,2 ethylene 4,4 dibenzoate) of Example 50 is crushed to a coarse powderand then heated under vacuum with a small bleed of nitrogen for 0.5 hourat 200 C., 0.5 hour at 210 C., 0.5 hour at 220 C., 1 hour at 230 C., 2.5hours at 240 C., and 0.5 hour at 225 C.

The PMT of the resulting polymer is 255 C. and the intrinsic viscosityis 1.0. The solid phase polymerized polymer is extruded at 290 C. toform a filament, using conventional techniques. The filament is orientedby drawing it 3.6x over a 127 C. pin. The drawn filament is heat treatedby boiling it in Water for minutes, heating it in an oven at 180 C. for3 minutes, and finally immersing it in boiling water again for 3minutes. The heat-treated filament is oriented and crystalline as shownby X-ray diffraction patterns. It has a tenacity of 2.3 g.p.d., anelongation of 28%, and an initial modulus of 26 g.p.d. Values for TSRand MRI, as defined in Example 4, are 69% and 0.074, respectively.

Oriented fibers are also prepared from the polyester of Example 47. Theyhave a tenacity of 0.6 g.p.d., an elongation of 15.5%, and an initialmodulus of 18.5 g.p.d. Oriented fibers prepared from the polyester ofExample 48 are tested for TSR and MRI and values for these parametersare found to be 69% and 0.03, respectively. Flexible films are meltpressed from the polyesters of Examples 45 and 49. The latter twopolyesters are also molded to form tough discs.

EXAMPLE 5 l Poly(bicyclohexyl-4,4-dimethylene adamantane- 1,3-dicarboxylate) Into a small polymer tube is placed 5.05 g. of dimethyladamantane-1,3-dicarboxylate (0.02 mol), 7.7 g. oft,tbis(4-hydroxymethylcyclohexyl) (0.034 mol), and 4 drops of an 8%solution of sodium hydrogen hexabutoxytitanate in n-butanol. Using thegeneral procedure of Example 4, ester exchange is carried out for 2hours at 220 C. and polycondensation is subsequently performed at 250280 C. for 3.5 hours under vacuum. The PMT of the resulting solid is 110C. The melting point of the polymer rises to 205 C. when it iscrystallized by treating the polymer with methylene chloride and dryingit.

The crystallized polymer is subjected to solid phase polymerization byheating it under vacuum with a small bleed of nitrogen beginning at 200C. and slowly raising the temperature to 240 C. over a period of severalhours. The PMT of the resulting polymer is 230 C. and the intrinsicviscosity is 0.4. Orientable fibers can be prepared from the melt.

EXAMPLE 52 Poly(bicyclohexyl-4,4'dimethylenedecahydronaphthalene-2,6-dicarboxylate) Into a small polymer tube isplaced 4.0 g. of dimethyl decahydronaphthalene 2,6 dicarboxylate (0.016mol), 7.2 g. of t,t bis(4 hydroxymethylcyclohexyl) (0.032 mol), and 3drops of an 8% solution of sodium hydrogen hexabutoxytitanate inn-butanol. Melt polymerization is carried out in the manner of Example4, yielding a polymer having a PMT of 125 C. and an intrinsic viscosityof 0.4. Flexible films are melt pressed from the polymer.

EXAMPLE 53 Poly(bicyclohexyl-4,4'-dimethylene dodecahydro- 4,4'-bibenzoate) This polyester is prepared by the general procedure for meltpolycondensation as in Example 4 by the reaction of dimethyl dodecahydro4,4 bibenzoate with t,t bis (4-hydroxymethyl)cyclohexyl. The polyesterhas a PMT of 237 and an intrinsic viscosity of 0.44 Orientable fibersare prepared from the melt.

EXAMPLE 54 Poly(bicyclohexyl-4,4-dimethylene 1,3-pr0pylene-4,4-bibenzoate) This polyester is prepared by melt polycondensation asin Example 4 from dimethyl 1,3-propylene-4,4'-dibenzoate a d pf-b t4- yy ethyl yc ch yll. It s. a us 20 ful molding material having a PMT of160 C. and an intrinsic viscosity of 0.43.

EXAMPLE 55 Poly(bicyclohexyl-4,4-dimethylene isopropylidene-4,4-dibenzoate) This polyester is prepared by melt polycondensation asin Example 4 from dimethyl isopropylidene-4,4'-dibenzoate andt,t-bis(4-hydroxyrnethylcyclohexyl). Its PMT is l65l95 C. and itsintrinsic viscosity is 0.31.

EXAMPLE 56 Poly(bicyclohexyl-4,4-dimethylene 1,2-ethylenebis[4-oxybenzoate] This polyester is prepared by melt polycondensation asin Example 4, with solid phase polymerization at 240 C. for 17 hours,from t,t-bis(4-hydroxymethylcyclohexyl) andl,Z-bis(4-carbomethoxyphenoxy)ethane. Its PMT is 283 C. and itsintrinsic viscosity is 0.77. Fibers spun and drawn in the conventionalmanner have a tenacity of 2.0 g.p.d., an elongation of 18%, and aninitial modulus of 28 g.p.d.

EXAMPLE 57 Poly('bicyclohexyl-4,4-dimethylene 2,5-dimethylterephthalate) This polyester is prepared by meltpolycondensation as in Example 4 from dimethyl 2,5-dimethylterephthalateand bis(4-hydroxymethylcyclohexyl) prepared as described in part G ofExample 1 (mixed geometrical isomers). Its PMT is C. and its intrinsicviscosity is 0.37.

EXAMPLE 58 Poly (bicyclohexyl-4,4'-dimethylene glutarate) This polyesteris prepared by melt polycondensation as in Example 4 from dimethylglutarate and t,t-bis(4-hy droxymethylcyclohexyl). Its PMT is 139 C. andits intrinsic viscosity is 0.63. Samples of the polyester are meltpressed to form flexible films and are molded into discs exhibitingexcellent toughness.

EXAMPLE 59 Segmented copolyesters of poly(bicyclohexyl-4,4'-dimethylene4,4-bibenzoate) and poly(2-methyl-2-ethyl-1,3- propylene terephthalate)A mixture of 35.5 g. of 2-rnethyl-2-ethyl-1,3-propanediol (0.3 mol),19.4 g. of dimethyl terephthalate (0.1 mol) and 1.0 ml. of a catalystsolution of 8% sodium hydrogen hexabutoxytitanate in n-butanol is heatedat 190-210 C. at atmospheric pressure for 5 hours with evolution ofmethanol. The pressure is then reduced to 0.7 mm. of mercury while thetemperature is maintained at 210 C., following which polycondensation iscarried out for 24 hours at this temperature and pressure. The product,poly- (2-methyl-2-ethyl-1,3-propylene terephthalate), has an intrinsicviscosity of 0.5 and a PMT of 104 C.

Dimethyl 4,4'-bibenzoate is reacted with 61% c,c-/ 35% c,t-/4%t,t-bis(4-hydroxymethylcyclohexyl) as in in Example 4 to formpoly(bicyclohexyl-4,4-dimethylene 4,4-bibenzoate) having an intrinsicviscosity of 0.61 and a PMT of 290 C. Eighty g. of the polymer is mixedwith 20 g, of the poly(2-methyl-2-ethyl-l,3-propylene terephthalate) ina -ml. round-bottom flask fitted with a glass stirrer and a nitrogeninlet. The flask is blanketed with nitrogen and heated to 300 C. Afterstirring for 10 minutes at this temperature and an additional 20 minutesat 320 C., the flask is allowed to cool. A segmented copolyester isobtained having an intrinsic viscosity of 0.45. The segmentedcopolyester is pulverized and heated at 220 C. and 0.2 mm. of mercuryfor 11 hours with a continuous slow stream of nitrogen gas passedthrough the powder from a capillary. The product has an intrinsicviscosity of 0.64 and a PMT of 233 C. Oriented fibers prepared from thepolymer have a tenacity of 1.3 g.p.d., an elongation of 25%, an initialmodulus of 23 g.p.d., a TSR of 67%, and an MRI of 0.17.

Another segmented copolyester is prepared, employing a 60% to 40% ratioby Weight of the two polyesters instead of the 80% to 20% ratio usedabove. In this instance a 40% c,t-, 60% t,tisomer mixture of bis-(4-hydroxymethylcyclohexyl) is used to prepare the poly-(bicyclohexyl-4,4-dimethylene 4,4-bibenzoate), which has a PMT of 305 C.and an intrinsic viscosity of 0.41; and 21 g. of this polymer is mixedwith 14 g. of the poly- (Z-methyl-Z-ethyl-l,3-propylene terephthalate).The mixture of polyesters is heated at 350 C. for 35 minutes withstirring, and the flask is then allowed to cool. The segmentedcopolyester has an intrinsic viscosity of 0.25 and a PMT of 170 C.

EXAMPLE 6O Segmented copolyester of poly(bicyclohexyl-4,4-dimethylene4,4-bibenzoate) and poly(2-methyl 2 ethyl-1,3- propylene azelate) Amixture of 108 g. of dimethyl azelate (0.5 mol) and 153 g. of2-methyl-2-ethyl-l,3-propandiol (1.3 mol) are heated with 0.4 g.tetrabutyl titanate at 170200 C. for 3.5 hours under nitrogen with theevolution of methanol. The pressure is then reduced to 0.5 mm. ofmercury and the temperature increased to 245 C. during a period of 35minutes, following which polycondensation is carried out for 24 hours atthis temperature and pressure. The product,poly(Z-methyl-Z-ethyl-1,3-propy1ene azelate), is liquid and has aninherent viscosity of 1.3. 2.8 g. Wt. percent) of this polyester is thenmixed with 25 g. (90 wt. percent) ofpoly(bicyclohexyl-4,4-dimethylene-4,4'- bibenzoate) having a PMT of 275C. and an intrinsic viscosity of 0.70, prepared from dimethyl4,4'-bibenzoate and 74% c,t-/ 26% t,t-bis(4 hydroxymethyleyclohexyl).The mixture of polyesters is heated for 10 minutes at 310 C. withstirring, after which the flask is cooled. The segmented copolyester hasan intrinsic viscosity of 0.60 and a PMT of 248 C.

EXAMPLE 61 Segmented copolyester of poly(bicycl0hexyl-4,4-dimethylene4,4'-bibenzoate) and poly(ethylene 2,5- dimethylterephth alate)Forty-four g. of dimethyl 2,5-dimethylterephthalate (0.198 mol) is mixedwith 37 g. (0.596 mol) of ethylene glycol in the presence of 0.1 g. oftetrabutyl titanate in 2 ml. of butanol. The mixture is heated at 180190C. for 3 hours with evolution of methanol. The pressure is then reducedto 0.6 mm. of mercury while the temperature is increased to 280 C.,following which polycondensation is carried out for 6.5 hours at thistemperature and pressure. The product, polyethylene2,5-dimethylterephthalate, has an inherent viscosity of 0.34 and a PMTof 92 C. Ten g. (20 wt. percent) of this polyester is then mixed with 40g. (80 wt. percent) of poly(bicyclohexyl- 4,4-dimethylene4,4-bibenzoate) having a PMT of 278 C. and an intrinsic viscosity of0.77, prepared from dimethyl, 4,4'-bibenzoate and 58% c,t-/42%t,t-bis(4- hydroxymethylcyclohexyl). The mixture of polyesters is heatedfor 47 minutes at 290 C. with stirring, after which the flask is cooled.The segmented copolyester has an intrinsic viscosity of 0.46 and a PMTof 270 C.

EXAMPLE 62 Segmented copolyester of polyethylene terephthalate andpoly(bicyclohexyl-4,4'-dime.thylene 2,5-dimethylterephthalate)Polyethylene terephthalate is prepared from a mixture of 4540 g. (23.2mols) of dimethyl terephthalate, 3064 g. of ethylene glycol (49.4 mols),13.6 g. of antimony troxide, and 20.4 g. of manganous acetate (4.5 H 0)by heating at 160320 C. for 2 hours at atmospheric pressure and then at266283 C. for 3 hours while the pressure is reduced to 1.8 mm. ofmercury. The product has a PMT of 255 C. and an intrinsic viscosity of0.68.

Forty g. Wt. percent) of polyethylene terephthalate is mixed with 10.0g. (20 wt. percent) of the poly- (bicyclohexyl-4,4-dimethylene2,5-dimethylterephthalate) of Example 57. The mixture of polyesters isheated for 30 minutes at 280 C. with stirring, after which the flask icooled. The segmented copolyesier has an intrinsic viscosity of 0.66 anda PMT of 242 C.

EXAMPLE 63 Polyesteramide of bis(4-hydroxymethy1cyclohexyl), 4,4-bibenzoic acid, terephthalic acid, and hexamethylenediamine Into a smallpolymer tube are placed 4.40 g. (0.01 mol) of N,Nbis(4-carbomethoxybenzoyl)hexamethylenediamine, prepared by reacting thehalf methyl ester, half acid chloride of terephthalic acid withhexamethylenediamine; 10.81 g. (0.04 mol) of dimethyl 4,4'-bibenzoate;11.88 g. (0.0525 mol) of 58% c,c-/36% c,t-/6% t,t-bis(4hydroxymethylcyclohexyl); and, as a catalyst, 0.5 ml. of an 8% solutionof sodium hydrogen hexabutoxytitanate in n butanol. The tube is heatedand a capillary flow of nitrogen is commenced. The reaction is carriedout under atmospheric pressure at 200 C. for 10 minutes, at 225 C. for20 minutes, and at 258 C. for 40 minutes, after which the pressure isreduced to 0.3 mm. of mercury and the tube is heated at 285 C. for 3hours. The molten polyesteramide is colorless and very viscous. Aftercooling, the product has a PMT of 259 C. and an intrinsic viscosity of0.99. Fibers melt-spun at 320 C. and drawn 3.3x are found to have atenacity of 2.5 g.p.d., an elongation of 14%, a modulus of 50 g.p.d.,and a TSR of 68.5%.

EXAMPLE 64 Polyesteramide of bis(4-hydroxymethylcyelohexyl),terephthalic acid, and hexamethylenediamine Into a small polymer tubeare placed 13.21 g. (0.03 mol) ofN,N-bis(4-carbomethoxybenzoyl)hexamethylenediamine, 7.13 g. (0.0315 mol)of 48% c,c-/44% c,t-/ 8% t,t-bis(4 hydroxymethylcyclohexyl), and, as acatalyst, 0.3 ml. of an 8% solution of sodium hydrogenhexabutoxytitanate in n-butanol. The tube is heated and a capillary flowof nitrogen is commenced. The reaction is carried out at atmosphericpressure at 200 C. for 10 minutes, at 225-235 C. for 40 minutes, and at285 C. for 40 minutes; after which the pressure is reduced to 0.3 mm. ofmercury and the temperature is maintained at 285 C. for 3 hours. Thepolyesteramide product has a PMT of 174 C. and an intrinsic viscosity of0.61. Orientable fibers are pulled from the melt.

EXAMPLE 65 Polyesteramide of bis(4-hydroxymethylcyclohexyl),hexamethylenediamine, and 4,4-bibenzoic acid Into a 3-neck flaskequipped with a mechanical stirrer, a thermometer, and a refluxcondenser are placed 13.5 g. (0.05 mol) of dimethyl 4,4-bibenzoate, 22.6g. (0.1 mol) of 58% c,c-/36% c,t-/6% t,t-bis(4-hydroxymethylcyclohexyl),3.7 g. of 79% aqueous hexamethylenediamine (0.025 mol of amine), and 25ml. of n-butanol. The mixture is heated and stirred at C. for 46 hours,after which the reflux condenser is replaced with a distilling head and27.0 g. (0.1 mol) additional dimethyl 4,4'-bibenzoate is added togetherwith 34.0 g. (0.15 mol) of the bis(4-hydroxymethylcyclohexyl). Thetemperature is increased to C. and maintained there until distillationceases, after which 2.7 ml. of 14.4% tetrabutyltitanate in n-butanol isadded. The mixture is then heated at 225 C. at atmospheric pressure for60 minutes, after which the pressure is reduced to 0.3 mm. of mercuryand the temperature is increased to 285 C.

23 for 2 hours. The product has a PMT of 271 C. and an intrinsicviscosity of 0.38.

Since many difierent embodiments of the invention may be made Withoutdeparting from the spirit and scope thereof, it to be understood thatthe invention is not limited by the specific illustrations except to theextent defined in the following claims.

I claim:

1. A crystalline linear polymeric fiber-forming polyester consistingessentially of recurring units of the following structural formula:

wherein m is or 1, n is I, Q and Q are saturated divalent hydrocarbonradicals of the group consisting of 1,3-cyclohexylene,1,4-cyclohexylene, and lower alkyl derivatives thereof; R is an alkyleneradical of up to 8 carbon atoms of which at most 4 carbon atoms are inthe chain connecting Q and Q; and A represents divalent hydrocarbonradicals selected from the group consisting of arylene, aralkylene orcycloalkylene radicals of up to 24 carbon atoms having the indicatedcarbonyl substituents attached directly to nuclear carbon atoms with thecarbonyl substituents separated by a chain of at least three nuclearcarbon atoms; said recurring units consisting essentially of units inwhich the radical A includes two 6-membered carbocyclic nuclei.

2. Fiber-forming polymeric polyester of a mixture consisting essentiallyof a bis(4-hydroxymethylcyclohexyl) alkane of 15 to 18 carbon atoms and4,4'-bibenzoic acid.

3. Fiber-forming polymeric polyester of a mixture consisting essentiallyof bis(4-hydroxymethylcyclohexyl) and dodecahydro-4,4-bibenzoic acid.

4. Fiber-forming polymeric polyester of a mixture consisting essentiallyof bis(4-hydroxymethylcyclohexyl) and 4,4-bibenzoicacid/decahydro-4,4-bibenzoic acid in the proportions of 90/10 to 25/75.

5. Fiber-forming polymer consisting essentially of poly(bicyclohexyl-4,4-dimethylene 4,4'-bibenzoate) 6. The polymer of claim 1in the form of a film.

7. The polymer of claim 1 in the form of a fiber.

8. Fiber-forming polymeric polyester of a mixture consisting essentiallyof bis(4-hydroxymethylcyclohexyl) methane and methylene-4,4-dibenzoicacid.

9. Fiber-forming polymeric polyester of a mixture consisting essentiallyof bis(4-hydroxymethylcyclohexyl) ethane and ethylene-4,4'-dibenzoicacid.

10. The polymer of claim 1 which is a polyester of bis(4-hydroxymethylcyclohexy1) and a dicarboxylic acid component comprisingat least mo] percent of 4,4- bibenzoic acid.

11. The polymer of claim 5 in the form of a fiber.

References Cited UNITED STATES PATENTS 3,227,682 1/1966 Hornbaker 2607SWILLIAM H. SHORT, Primary Examiner L. P. QUAST, Assistant ExaminerU.S.CI.X.R. 26047, 63, 178, 617

